CN106582319A - Method for preparing crystal film on non-woven fabric supporting body - Google Patents
Method for preparing crystal film on non-woven fabric supporting body Download PDFInfo
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- CN106582319A CN106582319A CN201611244567.9A CN201611244567A CN106582319A CN 106582319 A CN106582319 A CN 106582319A CN 201611244567 A CN201611244567 A CN 201611244567A CN 106582319 A CN106582319 A CN 106582319A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
Abstract
The invention belongs to the field of separation film preparing, and particularly relates to a method for preparing a crystal film on a non-woven fabric supporting body. The method comprises the following steps that S1, preprocessing is conducted on a macroporous structure and the surface of the non-woven fabric supporting body; S2, a seed crystal particle solution, a dispersant solution and a macromolecule organic material solution are mixed in proportion, a mixed solution is uniformly stirred and dispersed under the condition of ultrasonic water bath, and a thick macromolecule seed crystal suspension is prepared; S3, the macromolecule seed crystal suspension obtained in S2 adheres to the non-woven fabric supporting body obtained in S1 through a smeared method; and S4, the obtained non-woven fabric supporting body with the macromolecule seed crystal suspension adhering in S3 is placed in a film casting solution environment of the crystal film, a crystallization reaction of hydro-thermal synthesis is conducted, and after the reaction is finished, a crystal film product is taken out, washed and dried, namely the crystal film supported by the non-woven fabric is obtained. According to the method, the strict requirements for the supporting body and the particle size of the seed crystal in the crystal film preparing process are reduced, and production cost of the crystal film is reduced.
Description
Technical field
The invention belongs to separate field of membrane preparation, it is related to the preparation method of crystal film, more particularly to one kind in non-woven fabrics
The method that crystal film is prepared on support body.
Background technology
Membrane separation technique is a kind of new, efficient, purification and purification techniques, and the study hotspot of wherein crystal film mainly exists
Molecular screen membrane and MOF films.Molecular sieve is a kind of novel film materials that can realize molecule screening, and it has suitable with molecular size
And the aperture of uniformity, ion-exchange performance, high-temperature thermal stability performance, excellent shape selective catalysis performance and be easily modified and
It is available with different structure with various different types, it is preferable membrance separation and Membrane catalysis material.Metal organic frame
(MOFs) material has superhigh specific surface area and huge pore volume, the high-capacity storage of all kinds of gases is capable of achieving, while its aperture
The controllability of height regularity and surface group in structure is capable of achieving the high efficiency separation of multiple gases and liquid, and
Its material adsorption capacity and its dynamic performance can be substantially improved.MOF films are that in recent years numerous film scientific research personnel are particularly inorganic
The focus that film researcher is paid close attention to and studied.Its core is that design prepares high-quality stable MOF films, and realizes the key of this core
It is that, based on the growth film forming feature of MOF films, study science rational synthesis film-forming method.Before being had a wide range of applications due to it
Scape, the synthesis of MOF seperation films and applied research are increasingly becoming a focus in gas separation membrane field.
The synthetic method of crystal film has Vacuum-assisted method method, crystal seed method, plug-hole method, microwave heating method, pulse laser to sink
Area method and electrophoretic deposition etc..And existing crystal membrane preparation method is concentrated mainly on the aluminium oxide or rustless steel of lamellar or tubulose
On carrier, the coating of crystal seed is carried out using methods such as dip-coating, erasing or evacuations, then made completely by secondary crystallization synthesis step
Crystal film.NaA point of the crystal seed coating method synthesis that Chinese patent CN101381087A is rubbed using crystal seed and dipping combines
Sub- sieve membrane, such method exist crystal seed coating it is uneven, crystal seed is combined loosely with supporter, in preparation process to supporter with
The requirement of crystal seed particle diameter is harsh, and step is complicated, and aluminium oxide or rustless steel supporter are expensive, prepare the repetitive rate of dense molecular sieve membrane
Low shortcoming.Zhejiang University king is just precious, tight Yushan seminar adopts NaA molecular sieve/polyethers phenol (PES) composite hollow fibre conduct
Carrier prepares NaA molecular sieve membrane (J.Q.Li, J.Shao, Q.Q.Ge, Influences of the zeolite loading
and particle size in composite hollow fiber supports on properties of zeolite
NaA membranes.Micropor.Mesopor.Mater.160 (2012) 10-17), it is to avoid apply brilliant, can be in carrier surface
Form uniform crystal seed layer.Polymer P ES concentration is larger needed for the method, the NaA molecular sieve/PES composite hollow fibres of preparation
Carrier osmotic resistance is big, and mechanical strength is low, and the membrane module form of formation is single, because hollow-fibre membrane is easy in actual application
The characteristics of bending and cause the brittle failure of molecular sieve film layer.Similar, ZIFs film preparations synthesis also has many methods, its situ
Growth method is by substrate direct impregnation in Synthesis liquid, ZIFs films to be obtained after Crystallizing treatment, and in-situ synthesis are to substrate and conjunction
Requirement into condition is generally relatively stricter.Chinese patent CN201310136268.3 is as support using porous alumina carrier
The method that body prepares ZIF-8 films, this kind of method used carrier is expensive, complex steps, weight during crystal film is prepared
Renaturation is poor and scale amplifies more difficult.
The content of the invention
The technical problem to be solved in the present invention is that the aluminium oxide that in the market crystal membrane carrier is used or rustless steel are carried
Body is expensive, and the requirement in preparation process to supporter and crystal seed particle diameter is harsh, and production cost is higher, and membrane module form is single
The problems such as.The invention provides a kind of method that crystal film is prepared on non-woven fabrics supporter, this method reduces crystal film system
To supporter and the rigors of crystal seed particle diameter during standby, the production cost of crystal film is reduced, using non-woven fabrics supporter
Metamorphosis be capable of achieving the variation of crystal film product form.
The technical solution adopted for the present invention to solve the technical problems is：One kind prepares crystal film on non-woven fabrics supporter
Method, comprise the steps：
S1:Pretreatment is carried out to the macropore structure and surface of non-woven fabrics supporter；
S2：The solution of seed particles, dispersant and macromolecule organic material is mixed in proportion, mixed liquor is in ultrasound
Uniform stirring dispersion, makes thick macromolecule crystal seed suspension under conditions of water-bath.
S3：Macromolecule crystal seed suspension obtained by adhering to S2 on non-woven fabrics supporter as obtained by the method for coating in S1；
S4：The non-woven fabrics supporter that macromolecule crystal seed suspension is attached to obtained in S3 is placed in into the masking pendular ring of crystal film
In border, crystal film product is taken out, is cleaned, is dried by the crystallization of water-filling thermal synthesis of going forward side by side, reaction after terminating, that is, obtain with nothing
Cloth is spun to support crystal film.
Specifically, above-mentioned steps S1 specifically include following steps：
1) dry after non-woven fabrics are cleaned by ultrasonic respectively with pure water and alkali liquor；
2) in non-woven fabrics being impregnated into into water or methanol liquid, make duct hydraulically full；
3) nonwoven surface, absorption surface and the liquid near surface duct are wiped with Cotton Gossypii.
Jing often has the pollutant such as many impurity particles in the pore space structure of industrial non-woven fabrics, and these pollutant can affect height
Diffusion of the molecule crystal seed suspension inside non-woven fabrics, while causing the bad knot between macromolecule crystal seed suspension and non-woven fabrics
Close.So, first non-woven fabrics are cleaned in the method and ultrasound, to remove pollutant.Secondly, in coating macromolecule crystal seed
Before suspension, non-woven fabrics are carried out with the dipping of non-solvent (water or methanol) and is wiped on surface, it is intended that control macromolecule
Diffusion of the crystal seed suspension inside non-woven fabrics, to reach optimal coating effect.
Specifically, the non-woven fabrics in above-mentioned steps S1 are the resistant to elevated temperatures non-woven fabrics of acid and alkali-resistance, and its thickness is 0.4mm, is breathed freely
Rate is 6L/m2.s。
Specifically, it is flat or tubular type that the non-woven fabrics in above-mentioned steps S1 support volume morphing.
Specifically, seed particles are NaA type zeolite molecular sieve of the particle diameter distribution in 0.5-2 μ ms in above-mentioned steps S2
Or zeolite imidazole ester frame structure material (ZIF-8), its mass fraction is 0.5%-2%；Dispersant is poly- diethanol or poly- second
Alkene pyrrolidone, its mass fraction is 0.5%-2%；The solution of macromolecule organic material is surplus, the wherein organic material of macromolecule
Expect for polyether sulfone or polysulfones, its mass concentration is 9.5%-20.9%, solvent is N-Methyl pyrrolidone or dimethyl acetylamide.
Specifically, mixed liquor uniform stirring under conditions of ultrasonic water bath disperses 2 hours in above-mentioned steps S2, and keeps super
Sound bath temperature is 60 degrees Celsius.
Specifically, coating macromolecule crystal seed suspension on non-woven fabrics supporter in above-mentioned steps S3 uses thickness controllable
Flat Membrane scraper or tubular membrane coating equipment.
Specifically, in above-mentioned steps S4, the method for synthesizing NaA zeolite molecular sieve crystal film is Na in molar ratio2O:SiO2:
Al2O3:H2O=2:2:1:300 match somebody with somebody film making solution, in 100 degrees Celsius of lower crystallization 24 hours, after being dried on non-woven fabrics supporter
NaA molecular sieve membrane.
Specifically, in above-mentioned steps S4, the method for synthesizing ZIF-8 crystal films is ZnCl in molar ratio2:CHO2Na:C4H6N2:
CH3OH=2:2:3:500 make coating solution, at one hundred and twenty degrees centigrade crystallization 6 hours, and ZIF-8 on non-woven fabrics supporter is obtained after being dried
Molecular screen membrane.
The invention has the beneficial effects as follows：
1) it is high using macromolecule crystal seed suspension viscosity, in water the characteristics of rapid phase transition, dispersed and quick fixation
Seed particles, realize seed particles in the uniform stable inoculation of supporting body surface, it is to avoid the conventional numerous and diverse step for applying crystal method
Suddenly, crystal seed coats phenomenon uneven or that crystal seed cannot be fixed in supporting body surface.
2) the crystal high mechanical strength for preparing, good with supporter conjugation, such as the NaA molecular sieve membrane for being supported by non-woven fabrics
Crystal form is capable of achieving the variation of membrane module, such as tubular type, rolling, board-like, low price.
3) a kind of method that crystal film is prepared on non-woven fabrics supporter of the invention, the backing material for using is nonwoven
Cloth, nonwoven cloth material has the characteristics of aperture is big, porosity is high, so according to common lifting dipping inoculation crystallization, crystal seed without
Method is effectively fixed on the surface of non-woven fabrics supporter, and most of crystal seeds can come off or fall into the internal voids of non-woven fabrics, cause
During secondary crystallization grows, it is impossible to form complete crystal membrane structure in nonwoven surface；The present invention is in non-woven fabrics
The method that the coating inoculation of macromolecule crystal seed suspension is introduced during crystal film is prepared on support body, seed particles are dispersed in
In sticky macromolecular solution and dispersant system, macromolecule crystal seed suspension is attached to nonwoven surface by cladding process, then
The characteristics of meeting non-solvent rapid phase transition using macromolecule crystal seed suspension, by crystal seed non-woven fabrics supporting body surface is fixed on, and is solved
Non-woven fabrics cannot used as the problem of crystal film support.
4) a kind of method that crystal film is prepared on non-woven fabrics supporter of the invention, can directly adopt industrial nonwoven
Cloth is cheap as support body material, raw material sources extensively, simple to the pre-treatment of supporter in preparation process and crystal seed grain
The requirement in footpath is relatively low, fundamentally reduces production cost.
Description of the drawings
With reference to the accompanying drawings and examples the present invention is further described.
Fig. 1 is the simple schematic diagram of the crystal film preparation process that non-woven fabrics are supported；
Fig. 2 is on the non-woven fabrics supporter without pre-treatment of NaA seedings (being impregnated using NaA film crystallization synthesis mother liquid)
The scanning electron microscopic picture on surface；
Fig. 3 is the scanning of NaA seeding non-woven fabrics supporters (NaA film crystallization synthesis mother liquid dipping) prepared by embodiment 1
Electron microscopic picture (a) upper surface, (b) section；
Fig. 4 is NaA molecular sieve membrane scanning electron microscopic picture (a) upper surface with non-woven fabrics as support prepared by embodiment 3,
B () section (is removed after non-woven fabrics)；
Fig. 5 is the XRD figure piece of the NaA molecular sieve membrane that non-woven fabrics prepared by embodiment 2 are supported
Fig. 6 is the XRD figure piece of the ZIF-8 molecular screen membranes that non-woven fabrics prepared by embodiment 6 are supported.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further detailed explanation.
Embodiment 1
Choose thickness 0.4mm, air penetrability 6L/m2.s non-woven fabrics, are cleaned by ultrasonic respectively with pure water and alkali liquor, are dried
It is standby.NaA molecular sieve crystal that 0.1g mean diameters are 0.8 μm and 0.1g polyvinylpyrrolidones (PVP) are mixed into into 19.8g
Mass fraction is that the mixed liquor is in ultrasonic water bath in 9.5% polyether sulfone (PES) and the solution of N-Methyl pyrrolidone (NMP)
Under conditions of carry out uniform stirring and disperse 2 hours, and keep ultrasonic water bath temperature for 60 degrees Celsius, make NaA macromolecule crystal seeds
Suspension is standby.Meanwhile, with Ludox SiO2Aqueous solution is silicon source, NaAlO2For silicon source, NaOH is alkali source, in molar ratio Na2O:
SiO2:Al2O3:H2O=2:1:2:300 are configured to NaA film crystallization synthesis mother liquids.Additionally, non-woven fabrics are impregnated in water being allowed to
Full moistening, the non-woven fabrics after moistening are taken out with tweezers, and gently wipe the side that non-woven fabrics coat crystal seed with absorbent cotton.Above step
After the completion of, using scraper being coated in the NaA macromolecule crystal seed uniform suspensions for preparing on the surface of the non-woven fabrics, obtain
The non-woven fabrics supporter of NaA seedings.Again by ready NaA films crystallization synthesis mother liquid with NaA seeding non-woven fabrics supporters
It is positioned in Hydrothermal Synthesiss autoclave simultaneously, reacts 24 hours at a temperature of 100 degrees Celsius.React product after terminating
Take out and be washed with deionized to neutrality, it is the NaA for supporting subsequently to be dried in 50 degrees Celsius of baking oven and be able to non-woven fabrics
Molecular screen membrane.Crystal membrane structure that should be with non-woven fabrics as supporter is as shown in Figure 1.Fig. 2 show the not premenstrual place of NaA seedings
The non-woven fabrics of reason support the electron microscope of external surface, and by the visible NaA crystal seeds of the figure non-woven fabrics can be uniformly disperseed and be fixed on
Surface, but non-woven fabrics are not by the intact covering of macromolecule crystal seed suspension, still have nonwoven cloth silk shape thing exposed outside.Fig. 3 institutes
The non-woven fabrics through pre-treatment for being shown as NaA seedings support the electron microscope of external surface, and we can have found from Fig. 3 (a)
On the basis of NaA crystal seeds uniformly disperse and be fixed, non-woven fabrics obtain smooth crystal seed figure layer surface by intact covering.Figure
Section shown in 3 (b) can be found that thickness is rationally in macromolecule crystal seed suspension infiltration non-woven fabrics, the dispersion layer of nonwoven surface
Less than 10 microns, contribute to forming complete stable crystal film after diauxic growth.
Embodiment 2
By thickness 0.4mm, air penetrability 6L/m2.s non-woven fabrics make tubular type non-woven fabrics supporter, with pure water and alkali liquor point
It is not cleaned by ultrasonic, is dried standby.By NaA molecular sieve crystal that 0.5g mean diameters are 0.8 μm and the poly- diethanols of 0.5g
(PEG) in being mixed into the solution of polyether sulfone (PES) that 24g mass fractions are 20% and dimethyl acetylamide (DMAC), the mixing
Liquid carries out uniform stirring under conditions of ultrasonic water bath to be disperseed 2 hours, and keeps ultrasonic water bath temperature for 60 degrees Celsius, is made
NaA macromolecule crystal seed suspensions are standby.Meanwhile, with Ludox SiO2Aqueous solution is silicon source, NaAlO2For silicon source, NaOH is alkali source,
Na in molar ratio2O:SiO2:Al2O3:H2O=2:1:2:300 are configured to NaA film crystallization synthesis mother liquids.Additionally, tubular type non-woven fabrics
It is impregnated in water and is allowed to moisten completely, the tubular type non-woven fabrics supporter after moistening is taken out with tweezers, and pipe is gently wiped with absorbent cotton
Formula non-woven fabrics supporter will coat the outside of crystal seed.Next, using tubular membrane coating equipment by the NaA macromolecule crystals for making
Being coated on the outer surface of the non-woven fabrics for kind uniform suspension, obtains the tubular type non-woven fabrics supporter of NaA seedings.To prepare again
Good NaA film crystallization synthesis mother liquids are positioned in Hydrothermal Synthesiss autoclave simultaneously with NaA seeding non-woven fabrics supporters,
React 24 hours under 100 degree celsius temperatures.Product is taken out and is washed with deionized to neutrality, subsequently 50 by reaction after terminating
Degree Celsius baking oven in be dried and be able to non-woven fabrics be the NaA molecular sieve membrane for supporting, characterize for follow-up microstructure and XRD,
And carry out infiltration evaporation experiment.
Embodiment 3
Choose thickness 0.4mm, air penetrability 6L/m2.s non-woven fabrics, are cleaned by ultrasonic respectively with pure water and alkali liquor, are dried
It is standby.NaA molecular sieve crystal that 0.25g mean diameters are 1 μm and 0.2g polyvinylpyrrolidones (PVP) are mixed into into 24.6g
Mass fraction is that the mixed liquor is in ultrasonic water bath in 15% polyether sulfone (PES) and the solution of N-Methyl pyrrolidone (NMP)
Under the conditions of carry out uniform stirring and disperse 2 hours, and keep ultrasonic water bath temperature for 60 degrees Celsius, make NaA macromolecules crystal seed and hang
Supernatant liquid is standby.Meanwhile, with Ludox SiO2Aqueous solution is silicon source, NaAlO2For silicon source, NaOH is alkali source, in molar ratio Na2O:
SiO2:Al2O3:H2O=2:1:2:300 are configured to NaA film crystallization synthesis mother liquids.Additionally, non-woven fabrics are impregnated in water being allowed to
Full moistening, the non-woven fabrics after moistening are taken out with tweezers, and gently wipe the side that non-woven fabrics coat crystal seed with absorbent cotton.Next,
Using scraper being coated in the NaA macromolecule crystal seed uniform suspensions for preparing on the surface of the non-woven fabrics, immerse after standing
In water, the non-woven fabrics supporter of NaA seedings is obtained.Again by ready NaA films crystallization synthesis mother liquid with NaA seeding non-woven fabrics
Supporter is positioned in Hydrothermal Synthesiss autoclave simultaneously, reacts 24 hours under 100 degree celsius temperatures.Reaction will after terminating
Product takes out and is washed with deionized to neutrality, and it is what is supported to be subsequently dried in 50 degrees Celsius of baking oven and be able to non-woven fabrics
NaA molecular sieve membrane, characterizes for follow-up microstructure and XRD, and carries out infiltration evaporation experiment, its scanning electron microscopic picture such as Fig. 4
It is shown, wherein (a) upper surface, (b) section (removing after non-woven fabrics).
Embodiment 4
Choose thickness 0.4mm, air penetrability 6L/m2.s non-woven fabrics, are cleaned by ultrasonic respectively with pure water and alkali liquor, are dried
It is standby.ZIF-8 crystal grain that 0.1g mean diameters are 0.6 μm and 0.2g polyvinylpyrrolidones (PVP) are mixed into into 19.8g mass
Fraction is that the mixed liquor is under conditions of ultrasonic water bath in 10% polysulfones (PSF) and the solution of N-Methyl pyrrolidone (NMP)
Carry out uniform stirring to disperse 2 hours, and keep ultrasonic water bath temperature for 60 degrees Celsius, make ZIF-8 macromolecule crystal seed suspensions
It is standby.Meanwhile, ZnCl in molar ratio2:CHO2Na:C4H6N2:CH3OH=2:2:3:500 make ZIF-8 film crystallization synthetic solvents.
Additionally, be impregnated in methanol non-woven fabrics to be allowed to moisten completely, the non-woven fabrics after moistening are taken out with tweezers, and it is light with absorbent cotton
Wipe the side that non-woven fabrics coat crystal seed.Next, using scraper by the painting of the ZIF-8 macromolecule crystal seed uniform suspensions for preparing
Overlay on the surface of the non-woven fabrics, obtain the non-woven fabrics supporter of ZIF-8 seedings.Ready ZIF-8 films crystallization is synthesized again
Mother solution is positioned in Hydrothermal Synthesiss autoclave simultaneously with ZIF-8 seeding non-woven fabrics supporters, anti-under 120 degree celsius temperatures
Answer 6 hours.Product is taken out and is washed with deionized by reaction after terminating, and is subsequently dried in 80 degrees Celsius of baking oven and is able to
Non-woven fabrics are the ZIF-8 films for supporting, and are characterized for follow-up microstructure and XRD, circulation of qi promoting body separating experiment of going forward side by side.
Embodiment 5
By thickness 0.4mm, air penetrability 6L/m2.s non-woven fabrics make tubular type non-woven fabrics supporter, with pure water and alkali liquor point
It is not cleaned by ultrasonic, is dried standby.By ZIF-8 crystal grain that 0.5g mean diameters are 0.6 μm and 0.5g polyvinylpyrrolidones
(PVP) in being mixed into the solution of polysulfones (PSF) that 24g mass fractions are 20% and N-Methyl pyrrolidone (NMP), the mixed liquor
Uniform stirring is carried out under conditions of ultrasonic water bath to disperse 2 hours, and keeps ultrasonic water bath temperature for 60 degrees Celsius, make ZIF-
8 macromolecule crystal seed suspensions are standby.Meanwhile, ZnCl in molar ratio2:CHO2Na:C4H6N2:CH3OH=2:2:3:500 make ZIF-
8 film crystallization synthetic solvents.Additionally, be impregnated in water tubular type non-woven fabrics to be allowed to moisten completely, by the tubular type non-woven fabrics after moistening
Supporter is taken out with tweezers, and is gently wiped tubular type non-woven fabrics supporter with absorbent cotton and will be coated the outside of crystal seed.Next, using
The ZIF-8 macromolecule crystal seed uniform suspensions for making are coated in the outer of the tubular type non-woven fabrics supporter by tubular membrane coating equipment
On surface, the tubular type non-woven fabrics supporter of ZIF-8 seedings is obtained.Again by the same ZIF-8 of ready ZIF-8 films crystallization synthesis mother liquid
Seeding non-woven fabrics supporter is positioned in Hydrothermal Synthesiss autoclave simultaneously, reacts 6 hours at a temperature of 120 degrees Celsius.
Product is taken out and is washed with deionized by reaction after terminating, and is subsequently dried in 80 degrees Celsius of baking oven and is able to non-woven fabrics and is
The ZIF-8 films of support, characterize, circulation of qi promoting body separating experiment of going forward side by side for follow-up microstructure and XRD.
Embodiment 6
Choose thickness 0.4mm, air penetrability 6L/m2.s non-woven fabrics, are cleaned by ultrasonic respectively with pure water and alkali liquor, are dried
It is standby.ZIF-8 crystal grain that 0.25g mean diameters are 0.6 μm and 0.25g polyvinylpyrrolidones (PVP) are mixed into into 24.5g matter
Amount fraction is condition of the mixed liquor in ultrasonic water bath in 15% polysulfones (PSF) and the solution of N-Methyl pyrrolidone (NMP)
Under carry out uniform stirring and disperse 2 hours, and keep ultrasonic water bath temperature for 60 degrees Celsius, make the suspension of ZIF-8 macromolecules crystal seed
Liquid is standby.Meanwhile, ZnCl in molar ratio2:CHO2Na:C4H6N2:CH3OH=2:2:3:500 make ZIF-8 films crystallization synthesizes molten
Liquid.Additionally, be impregnated in methanol non-woven fabrics to be allowed to moisten completely, the non-woven fabrics after moistening are taken out with tweezers, and with absorbing water
Cotton gently wipes the side that non-woven fabrics coat crystal seed.Next, using scraper by the ZIF-8 macromolecule crystal seed uniform suspensions for preparing
Be coated on the surface of the non-woven fabrics, obtain the non-woven fabrics supporter of ZIF-8 seedings.Again by ready ZIF-8 films crystallization
Synthesis mother liquid is positioned in Hydrothermal Synthesiss autoclave simultaneously with ZIF-8 seeding non-woven fabrics supporters, 120 degrees Celsius of temperature
The lower reaction of degree 6 hours.Product is taken out and is washed with deionized by reaction after terminating, and is subsequently dried in 80 degrees Celsius of baking oven
And it is the ZIF-8 films for supporting to be able to non-woven fabrics, characterize for follow-up microstructure and XRD, circulation of qi promoting body separating experiment of going forward side by side.
Table 1 is the infiltration evaporation reality that the NaA molecular sieve membrane that non-woven fabrics prepared by embodiment 1-3 are supported is applied to ethanol dehydration
Test result.Raw material is 90% ethanol/water mixed solution, and experimental temperature is 80 degrees Celsius, and vacuum is 500 Pascals.
Table 1：The NaA molecular sieve membrane ethanol dehydration infiltration evaporation experimental result that non-woven fabrics are supported
| Embodiment | Separation factor | Total flux (Kg/m2.h) |
| 1 | ＞ 10000 | 11.5 |
| 2 | ＞ 10000 | 9.5 |
| 3 | ＞ 10000 | 10.8 |
Table 2 is that the ZIF-8 films that non-woven fabrics prepared by embodiment 4-6 are supported are applied to the detached experimental result of gas.Experiment
Tested at room temperature from pure hydrogen, carbon dioxide and nitrogen, inlet end gauge about 30psi.
Table 2：The ZIF-8 film gas separating experiment results that non-woven fabrics are supported
With the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Entirely various change and modification can be carried out in the range of without departing from this invention technological thought.The technology of this invention
Property scope is not limited to the content in description, it is necessary to its technical scope is determined according to right.
Claims (9)
1. it is a kind of on non-woven fabrics supporter prepare crystal film method, it is characterised in that comprise the steps：
S1:Pretreatment is carried out to the macropore structure and surface of non-woven fabrics supporter；
S2：The solution of seed particles, dispersant and macromolecule organic material is mixed in proportion, mixed liquor is in ultrasonic water bath
Under conditions of uniform stirring dispersion, make thick macromolecule crystal seed suspension.
S3：Macromolecule crystal seed suspension obtained by adhering to S2 on non-woven fabrics supporter as obtained by the method for coating in S1；
S4：The non-woven fabrics supporter that macromolecule crystal seed suspension is attached to obtained in S3 is placed in into the preparation liquid environment of crystal film
In, crystal film product is taken out, is cleaned, is dried by the crystallization of water-filling thermal synthesis of going forward side by side, reaction after terminating, that is, obtain with nonwoven
Cloth is support crystal film.
2. a kind of method that crystal film is prepared on non-woven fabrics supporter as claimed in claim 1, it is characterised in that：The step
Rapid S1 specifically includes following steps：
1) dry after non-woven fabrics are cleaned by ultrasonic respectively with pure water and alkali liquor；
2) in non-woven fabrics being impregnated into into water or methanol liquid, make duct hydraulically full；
3) nonwoven surface, absorption surface and the liquid near surface duct are wiped with Cotton Gossypii.
3. a kind of method that crystal film is prepared on non-woven fabrics supporter as claimed in claim 2, it is characterised in that：The step
Non-woven fabrics in rapid S1 are the resistant to elevated temperatures non-woven fabrics of acid and alkali-resistance, and its thickness is 0.4mm, and air penetrability is 6L/m2.s。
4. a kind of method that crystal film is prepared on non-woven fabrics supporter as claimed in claim 1, it is characterised in that：The step
It is flat board or tubular type that non-woven fabrics in rapid S1 support volume morphing.
5. a kind of method that crystal film is prepared on non-woven fabrics supporter as claimed in claim 1, it is characterised in that：The step
Seed particles are NaA type zeolite molecular sieve or zeolite imidazole ester framing structure of the particle diameter distribution in 0.5-2 μ ms in rapid S2
Material (ZIF-8), its mass fraction is 0.5%-2%；Dispersant is poly- diethanol or polyvinylpyrrolidone, its mass fraction
For 0.5%-2%；The solution of macromolecule organic material is surplus, and wherein macromolecule organic material is polyether sulfone or polysulfones, its matter
Amount concentration is 9.5%-20.9%, and solvent is N-Methyl pyrrolidone or dimethyl acetylamide.
6. a kind of method that crystal film is prepared on non-woven fabrics supporter as claimed in claim 1, it is characterised in that：The step
Mixed liquor uniform stirring under conditions of ultrasonic water bath disperses 2 hours in rapid S2, and keeps ultrasonic water bath temperature to be 60 degrees Celsius.
7. a kind of method that crystal film is prepared on non-woven fabrics supporter as claimed in claim 1, it is characterised in that：The step
Macromolecule crystal seed suspension is coated in rapid S3 on non-woven fabrics supporter to apply using the controllable Flat Membrane scraper of thickness or tubular membrane
Coating equipment.
8. a kind of method that crystal film is prepared on non-woven fabrics supporter as claimed in claim 5, it is characterised in that：The step
In rapid S4, the method for synthesizing NaA zeolite molecular sieve crystal film is Na in molar ratio2O:SiO2:Al2O3:H2O=2:2:1:300 match somebody with somebody
Film making solution, in 100 degrees Celsius of lower crystallization 24 hours, after being dried NaA molecular sieve membrane on non-woven fabrics supporter.
9. a kind of method that crystal film is prepared on non-woven fabrics supporter as claimed in claim 5, it is characterised in that：The step
In rapid S4, the method for synthesizing ZIF-8 crystal films is ZnCl in molar ratio2:CHO2Na:C4H6N2:CH3OH=2:2:3:500 make
Coating solution, at one hundred and twenty degrees centigrade crystallization 6 hours, obtain ZIF-8 molecular screen membranes on non-woven fabrics supporter after being dried.
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| CN108295672A (en) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of metal organic framework ZIF-8 films |
| CN108465385A (en) * | 2018-03-13 | 2018-08-31 | 中山大学 | A kind of MAF-4 metallic organic frame films and its application |
| CN109351212A (en) * | 2018-12-27 | 2019-02-19 | 刘庆玉 | A kind of polysulfone ultrafiltration membrane and its application in drink water purifying, reusing sewage field |
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| CN108295672A (en) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of metal organic framework ZIF-8 films |
| CN108295672B (en) * | 2017-01-12 | 2020-08-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of metal organic framework ZIF-8 film |
| CN108465385A (en) * | 2018-03-13 | 2018-08-31 | 中山大学 | A kind of MAF-4 metallic organic frame films and its application |
| CN108465385B (en) * | 2018-03-13 | 2021-09-03 | 中山大学 | MAF-4 metal organic framework film and application thereof |
| CN109351212A (en) * | 2018-12-27 | 2019-02-19 | 刘庆玉 | A kind of polysulfone ultrafiltration membrane and its application in drink water purifying, reusing sewage field |
| CN109433028A (en) * | 2018-12-27 | 2019-03-08 | 刘庆玉 | A kind of polyamide reverse osmose membrane and its application in field of seawater desalination |
| CN109433031A (en) * | 2018-12-27 | 2019-03-08 | 刘庆玉 | A kind of poly (ether-sulfone) ultrafiltration membrane and its application in haemodialysis field |
| CN109433031B (en) * | 2018-12-27 | 2021-07-09 | 青岛市中医医院(青岛市海慈医院、青岛市康复医学研究所) | Polyether sulfone ultrafiltration membrane and application thereof in field of hemodialysis |
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| CN110777537A (en) * | 2019-11-04 | 2020-02-11 | 北京理工大学 | ZIF-8/non-woven fabric composite material and preparation method thereof |
| CN113209839A (en) * | 2021-05-11 | 2021-08-06 | 天津工业大学 | Mixed matrix membrane with high acid resistance for methane/nitrogen separation, and preparation method and application thereof |
| CN113209839B (en) * | 2021-05-11 | 2022-03-08 | 天津工业大学 | Mixed matrix membrane with high acid resistance for methane/nitrogen separation, and preparation method and application thereof |
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